EP0120242B1 - Process for coating a substrate with polyimide - Google Patents

Process for coating a substrate with polyimide Download PDF

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Publication number
EP0120242B1
EP0120242B1 EP84101277A EP84101277A EP0120242B1 EP 0120242 B1 EP0120242 B1 EP 0120242B1 EP 84101277 A EP84101277 A EP 84101277A EP 84101277 A EP84101277 A EP 84101277A EP 0120242 B1 EP0120242 B1 EP 0120242B1
Authority
EP
European Patent Office
Prior art keywords
oligomer
diester
alcohol
molecular weight
tetracarboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84101277A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0120242A1 (en
Inventor
James Economy
Willi Volksen
Do Yeung Yoon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0120242A1 publication Critical patent/EP0120242A1/en
Application granted granted Critical
Publication of EP0120242B1 publication Critical patent/EP0120242B1/en
Expired legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide

Definitions

  • This invention is concerned with a process for coating a substrate with polyimide.
  • US-A-3,565,549 is concerned with reinforced laminates, and discloses the preparation of polyimide prepolymer and its subsequent curing. That patent specification lists numerous polyfunctional amines and polyfunctional anhydrides which may be used to prepare polyimides. The specification also contains a summary of the prior art. US-A-3,745,149, also discloses curing of a prepolymer.
  • US-A-3,726,834 is concerned with polyimides prepared from two or more aromatic diamines at least one of which is meta-substituted.
  • EP-A-0053927 discloses a process for making a high molecular weight polyimide by heating a chilled solution containing a diamine-terminated polyamide acid prepolymer, a tetracarboxylic acid dianhydride finishing component, and a converting system (such as a lower fatty acid anhydride) to form a polyamide acid polymer which is concurrently converted to a polyimide.
  • a converting system such as a lower fatty acid anhydride
  • the invention seeks to provide a process which is easily carried out and yields a coating simultaneously having good planarisation and good mechanical and thermal stability.
  • a process for coating a substrate with polyimide comprises the successive steps of applying an amido-oligomer having terminal amino groups and a diester to the substrate, the oligomer being formed from an aromatic diamine and from an aromatic dianhydride and the diester being formed from an aromatic tetracarboxylic acid and an alcohol, reacting the oligomer and the diester in situ at a temperature between 40°C and 140°C so that the diester reacts with the terminal amino groups of the oligomer to form a high molecular weight polyamide and curing the product of the reaction to form a cyclic imide.
  • the ester must be one which reacts with an amine group of the amino terminated oligomer to form a high molecular weight polyamide at a temperature between 40°C and 140°C, and which continues to react to form a cyclic imide.
  • the preferred esters which meet these requirements are those from alcohols which are activated by being substituted with an electron withdrawing group.
  • the most preferred alcohols are CF 3 -CH 2- OH and
  • Other useful alcohols include, for example, hydroxy-acetone, trichloroethanol, 1,3-difluoro-2-propanol, ethyl-2 - hydroxyiso butyrate and diethyl tartronate, or in fact any alcohol which yields an ester which will react to form a polyamide within the range of 40-140°C.
  • the aromatic tetracarboxylic acid portion of the ester may be from any of such acids known in the art, and shown, for example, in the patents referred to above.
  • Preferred acids include pyromellitic acid and benzophenone tetracarboxylic acid.
  • the aromatic diamine portion of the original reactants may be any of the aromatic diamine known to the art and referred to in the above patents.
  • the most preferred material is oxydianiline.
  • the prepolymer is preferably applied to the substrate in the form of a solution in a solvent.
  • solvents include, for example, polar organic solvents such as N-methyl pyrolidone, DMSO (Dimethylsulfoxide), Dimethyl acetamide, Dimethyl formamide and mixtures with other solvents.
  • an amido-oligomer having terminal amino groups is used in the present invention at a temperature of from 40°C to 140°C, there occurs a reaction between the ester and the amine group to form a high molecular weight polyamide, and reaction continues to form a cyclic amide. It is preferred that the oligomer have an initial molecular weight between 500 and 10,000, and most preferably between 1,000 and 5,000.
  • the dichloromethane was removed by means of a rotary evaporator yielding the triethylammonium salt of the desired diester as a viscous, amorphous mass.
  • This material was then dissolved in approximately 750 ml of distilled water and the solution gradually added to cold, dilute aqueous HCI causing the desired product to precipitate as a white, flocculant mass. This was immediately filtered and thoroughly washed with distilled water. Drying of the product in vacuo at 60 degrees C for 24 hours gave the pyromellitic acid ethylglycolate diester in quantitative yield.
  • NMR characteristics of the product in a mixture of deuterated chloroform and dimethylsulfoxide exhibited a multiplet at 8.2 ppm, a singlet at 4.8 ppm, a quartet at 4.2 ppm and a triplet at 1.2 ppm in the ratio of 1:2:2:3 in accordance with the projected spectrum of the desired product.
  • the amorphous residue was dissolved in 250 ml of distilled water and added to a cold, dilute aqueous HCI solution causing the precipitation of a non-crystalline material.
  • the supernatant was decanted and thoroughly extracted with diethyl ether and the remaining amorphous precipitate also dissolved in diethyl ether.
  • the ether fractions were combined and dried over calcium chloride. Filtration and evaporation of the diethyl ether gave an off-white crystalline material in approximately 60% yield.
  • NMR characterisation of the product in a mixture of deuterated chloroform/dimethylsulfoxide exhibited a multiplet at 8.1 ppm, a quartet at 5.2 ppm, in the ratio of 2:1:2:3:3 consistent with the projected spectrum of the desired product.
  • NMR characterisation of the product in deuterated acetone exhibited a multiplet at 8.1 ppm, a multiplet at 4.3 ppm, and a multiplet of peaks at 1.7 and 1.0 ppm in the ration of 1:2:3:6 in accordance with the desired structure.
  • DP refers to the degree of polymerization and is the number of amide bonds per oligomer unit.
  • the polymerization mixture was stirred vigorously and stirring was continued for 3 days until the polymerization mixture had become homogeneous.
  • the resulting viscous solution was next aged for 2 weeks at ambient temperature, sealed in sample bottles and stored in a refrigerator. All operations were performed under the exclusion of moisture, and oxygen in an environmental chamber, yielding the oligomer solution ready for further formulation with the diester at a total solids content of approximately 25 wt%.
  • the above illustrated formulations were spun-cast onto glass slides and cured to elevated temperatures under a nitrogen atmosphere.
  • the curing temperature profile started at 50°C and proceeded at 5°/min to 100°C where the temperature was held for one hour.
  • the specimen was heated to 135°C at 5°/min and held at this temperature for two hours.
  • the temperature was slowly raised at 0.5°/min to a final temperature of 400°C.
  • Removal of the cured films from the glass substrate and examination of the films by IR spectroscopy revealed spectra identical to the polyimide obtained from thermally curing high molecular weight polyamic-acid based on the same monomers (pyromellitic dianhydride and oxydianiline).
  • Sample No. 1 is a commercially available high molecular weight polyamic acid based on PMDA-ODA pyromellitic dianhydride and oxydianiline.
  • Sample No. 2 is the formulation based on ethyl glycolate, as prepared above.
  • Sample No. 3 is the formulation based on trifluoroethanol, as prepared above.
  • Sample No. 4 is the formulation based on iso-amyl alcohol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)
EP84101277A 1983-03-29 1984-02-08 Process for coating a substrate with polyimide Expired EP0120242B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US480164 1983-03-29
US06/480,164 US4467000A (en) 1983-03-29 1983-03-29 Process for coating a substrate with polyimide

Publications (2)

Publication Number Publication Date
EP0120242A1 EP0120242A1 (en) 1984-10-03
EP0120242B1 true EP0120242B1 (en) 1987-01-07

Family

ID=23906904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84101277A Expired EP0120242B1 (en) 1983-03-29 1984-02-08 Process for coating a substrate with polyimide

Country Status (4)

Country Link
US (1) US4467000A (enrdf_load_stackoverflow)
EP (1) EP0120242B1 (enrdf_load_stackoverflow)
JP (1) JPS59179667A (enrdf_load_stackoverflow)
DE (1) DE3461935D1 (enrdf_load_stackoverflow)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4528216A (en) * 1983-02-24 1985-07-09 Oki Electric Industry Co., Ltd. Process for forming heat-resistant resin films of polyimide and organosilicic reactants
FR2568258B1 (fr) * 1984-07-25 1987-02-13 Inst Francais Du Petrole Compositions de precurseurs de polyimides, leur preparation, les polyimides en derivant et leurs utilisations, notamment dans la fabrication de vernis d'emaillage pour conducteurs electriques
US4562100A (en) * 1984-09-14 1985-12-31 E. I. Du Pont De Nemours And Company Polyimide coating compositions from diesterified anhydride and aromatic diamine
US4612210A (en) * 1985-07-25 1986-09-16 International Business Machines Corporation Process for planarizing a substrate
JPH0727966B2 (ja) * 1986-07-04 1995-03-29 日立化成工業株式会社 半導体装置
US4849501A (en) * 1988-04-19 1989-07-18 International Business Machines Corporation Polyimide coating compositions based on meta-dialkyldihydrogen pyromellitate and aromatic diamines
US5026822A (en) * 1988-07-12 1991-06-25 Hoechst Celanese Corp. High molecular weight polyimide, method of making same and articles formed therefrom
US5049649A (en) * 1988-07-12 1991-09-17 Hoechst Celanese Corp. Colorless films formed from fluorinated polyimides
JPH0253827A (ja) * 1988-08-17 1990-02-22 Kanegafuchi Chem Ind Co Ltd ポリイミド共重合体
DE3927498C2 (de) * 1989-08-21 2002-01-17 Merck Patent Gmbh Polyamidester, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Polyimiden
US5153307A (en) * 1991-07-31 1992-10-06 International Business Machines Corporation Stabilization of polyamide alkyl ester solutions
JPH05331443A (ja) * 1992-06-02 1993-12-14 Sumitomo Bakelite Co Ltd フィルム状接着剤
WO2001081453A1 (en) * 2000-04-27 2001-11-01 Virginia Tech Intellectual Properties, Inc. Method for making polyimide
KR101544112B1 (ko) * 2004-03-03 2015-08-12 군제 가부시키가이샤 무단의 관 모양 폴리이미드 필름

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347808A (en) * 1966-07-05 1967-10-17 Monsanto Co Coating compositions
BE693296A (enrdf_load_stackoverflow) * 1967-01-27 1967-07-03
US3565549A (en) * 1968-06-20 1971-02-23 Trw Inc Process for preparing reinforced resinous structures
US3745149A (en) * 1971-09-29 1973-07-10 Nasa Preparation of polyimides from mixtures of monomeric diamines and esters of polycarboxylic acids
US3726834A (en) * 1972-07-03 1973-04-10 Int Harvester Co Thermoplastic copolyimides
US3998786A (en) * 1973-05-25 1976-12-21 University Of Notre Dame Du Lac Process for preparing aromatic polyimides, polyimides prepared thereby

Also Published As

Publication number Publication date
DE3461935D1 (en) 1987-02-12
US4467000A (en) 1984-08-21
EP0120242A1 (en) 1984-10-03
JPS59179667A (ja) 1984-10-12
JPH0159305B2 (enrdf_load_stackoverflow) 1989-12-15

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